H19 4 4 -

“Principles of Bioinorganic Chemistry”, S. J. Lippard, J. M. Berg

Heme Protein

Ferredoxin

Fe

Cu

Zn

Plastocyanin

0.6e

he

0.5e h

(1) suitable molecular arrangement and frontier MOpermitting the formation of conduction band

(2) carrier generation by using charge transfer betweenthe molecules forming conduction band and otherchemical species

Requirements for design of mol. metals

(TMTSF)2PF6 (TTF)(TCNQ)

decreasing Tascending Tafter 24 hours at 360 C

Metal-free phtalocyanine

1.4

-1

-21.6 1.8

1

0

1000/T

log

(R/ M

W)

Organic Semiconductors

H. Akamatu and H. Inokuchi, J. Chem. Phys., 18, 810 (1950).

ViolanthroneR288K = 2.3 x 1010 cm

Ea = 0.39 eV

Iso-ViolanthroneR288K = 5.7 x 109 cm

Ea = 0.375 eV

25 30 351/T (x104 degree-1)

Log 1

0

8

9

10D. D. Eley, Nature, 162, 819 (1948).

Violanthrone Iso-Violanthrone

= 0 exp E/RT

First Single-component Molecular Metal Ni(tmdt)2

S

S

S

S

SNi

S

S

S

S

S

S

S

Single-component Molecular Metals (Conductors)

2. Au(tmdt)2

3. Cu(dmdt)2 4. Zn(tmdt)2

5. Co(dt)2

1. Ni(tmdt)2

S

S

S

S

SNi

S

S

S

S

S

S

S

S

S

S

S

SAu

S

S

S

S

S

S

S

S

S

S

S

SZn

S

S

S

S

S

S

S

S

S

S

S

SCu

S

S

S

S

S

S

S

Me

MeMe

Me

S

S

S

S

SCo

S

S

S

S

S

S

S

2

Metallic Crystals composed of Single-component MoleculesH. Tanaka, Y. Okano, H. Kobayashi, W. Suzuki, A. Kobayashi,Science, 291, 285 (2001).

0

1.0

2.0

3.0

(x 10-4)4.0

0 100 200 300T (K)

(emu·m

ol -1)

10-3

10-2

R (

)

Metallic down to 0.5 Krt = 400 S·cm-1

[Ni(tmdt)2]S

S

S

S

SNi

S

S

S

S

S

S

S

The observation of dHvA oscillation(510 Tesla ~ 10% of the 1st Brillouin zone)

a*

[Ni(tmdt)2] b*

H. Tanaka, M. Tokumoto (AIST), J. Brooks(NHMFL/FSU) 1st principles density functional calculation......E. Canadell et al.

S

S

S

S

SNi

S

S

S

S

S

S

S

S. Ishibashi

c*C*c*a*

b*

100 µm~ 0.5 µg 1 mm

Observed and calculated angular dependences of the dHvAfrequencies

Hole(blue) and electron(red) Fermi surfaces

Y. Okano

H. Tanaka, M. Tokumoto, J. Brooks, et al. JACS, 2004, 126, 10518.

Observation of 3D Fermi Surfaces in [Ni(tmdt)2]

Torque magnetometry of [Ni(tmdt)2]

Symmetry of frontier MOHOMO of TTF-donor

HOMO

LUMO

l+ r

b1u

b2g

HOMO of TTN

nodal plane

E

l- r (+cdxz)

Ni(dmdt)2l E 2kS

Parallel band

Molecular Design of Metallic Crystal Based on

Intramolecular Electron Transfer between HOMO and LUMO Bands

Parallel band Crossing band

HOMOHOMO

LUMOLUMO

WLWH

WL

WH

e hE

a) Small HOMO-LUMO gap

b) Strong intermolecular interactions

Small Fermi surfaces [(Semi)metal]

Large Fermi surfaces (Metal)

C=C….bonding S-C….antibonding

Bond lengths of [Ni(tmdt)2]n-

LUMO

Comparison of bond lengths between [M(ligand)2]0 and [M(ligand)2]2-

abdc

egh

fi

-2 0-26-2513-17-18

-2116

i

planar

LUMO

HOMO

cf

i

abcdefghi

2.287(1)1.738(3)1.341(4)1.766(3)1.756(3)1.342(5)1.758(3)1.748(3)1.330(5)

2.282(1)1.683(4)1.414(9)1.743(4)1.738(4)1.361(7)1.737(4)1.762(4)1.353 (9)

-5-5573-23-1820-211423

n=2 n=

Bond lengths of [Cu(dmdt)2]n-

Tetrahedral

Ar =

2

4 612

Ref. W. Suzuki, E. Fujiwara, A. Kobayashi, Y. Fujishiro, E. Nishibori, M. Takata, M. Sakata, H. Fujiwara, H. Kobayashi, J. Am. Chem. Soc., 125, 1486 (2003).

[NiL[NiL22]]22-- [NiL[NiL22]]-- [NiL[NiL22]]00

[AuL[AuL22]]-- [AuL[AuL22]]00

--ee----ee--

--ee--

[M(tmdt)2] (M = Ni, Au) are isostructural to each other.

[Au(tmdt)[Au(tmdt)22] (] (MM == AuAu3+3+))

Crystal Structure of [Au(tmdt)Crystal Structure of [Au(tmdt)22]]

Bu4N[Au(tmdt)2]

[Au(tmdt)2]

Photon Factory, High Energy Accelator Research Organization

H. Kondo & T. Ohta( The Univ. Tokyo)

nBu4N[Au(tmdt)2]

[Au(tmdt)2]

0.51

1.52

2.53

3.5

010203040506070

0 100 200 300

1/T 1

(sec

-1)

(2nd Mom

ent) 1/2 (kHz)

T (K)

-2

-1.5

-1

-0.5

0 5 10 15 20

log

1000/T

110 K

-2

-1.5

-1

-0.5

0 5 10 15 20

log

1000/T

110 K

rt = 50 S·cm-1,Ea = 16 meV

Compressed pellet sample

Physical PPhysical Propertiesroperties of [Au(tmdt)of [Au(tmdt)22]]

By: E. Fujiwara (Tokyo Univ.)By: H. Tanaka, S. Hara, M. Tokumoto (AIST)

(SQUID)…powder sample

Au(tmdt)2

T > TN p = 4.0 x10-4 eum/mol

T < TN = AF local moment + pAF local moment = 3 AFpowder

=3.0 x10-4 emu /mol at TN…mag. moment= 0.30 B

(g=2.0, S=1/2)

p (T

(LDA result) Local Density Approximation and ab initio plane-wave norm-conserved pseudopotential method

as electron surface

from 84th band

as hole surface

a*

b*

c*a*

b*

c*

a*

b*

c*a*

b*

c*

Fermi surface of Au(tmdt)2 S. Ishibashi (AIST) K. Terakura (Hokkaido Univ.)

for Au(tmdt)2kkqkqkkq d

EEEfEf

BZnn

nn 1)(0

0.0 0.2 0.40.6

0.81.0 0.0

0.20.4

0.60.8

1.0

0(q

)

q b(/b

*)

qa (/a*)

0.0 0.2 0.40.6

0.81.0 0.0

0.20.4

0.60.8

1.0

(q)

q c(/c

*)

qa (/a*)

S. Ishibashi (AIST) K. Terakura (Hokkaido Univ.)

Lattice Parameter Variety of TemperatureLattice Parameter Variety of Temperature

PowderPowder

By: D. Kawaguti, S. Aoyagi, E. Nishibori, M. Sakata (Nagoya Uinv.) By: M. Maeyama (Rigaku)

MICROMax007/VariMax/Saturn

Single CrystalSingle Crystal

300 K 200 K

130 K 90 K

1.359

S

2.306

91.64Au

1.758

3.308 1.355

S

2.318

91.10Au

1.736

3.309

1.363

S

2.320

91.10Au

1.754

3.313 1.364

S

2.317

91.60Au

1.754

3.323

Crystal Structure of Au(tmdt)Crystal Structure of Au(tmdt)22 at Low Temperatureat Low Temperature

NewNew ESRESR of [Au(tmdt)of [Au(tmdt)22]]B. Zhou (Univ. Tokyo, Nihon Univ.)

[Cu(dmdt)2]High room temperature conductivity

( rt = 3 S·cm-1, Ea = ~40 meV)Curie-Weiss like magnetic susceptibility

(C = 0.33 emu·K·mol-1, = -4.2 K)

H. Tanaka, H. Kobayashi, A. Kobayashi, J. Amer. Chem. Soc. 124, 10002 (2002)

S

S

S

S

SCu

S

S

S

S

S

S

S

Me

MeMe

Me

Magnetic conductorconsists of single-component molecule

Crystal size 0.05 x 0.05 x 0.02 mm3Rigaku MERCURY CCD system

C16H12S12Cu monoclinic C 2/ca = 24.27(1) Åb = 8.250(6) = 91.38(1)c = 11.500(8) V = 2299(2) Å3 Z = 4R = 0.065

Molecular arrangement of [Cu(dmdt)Molecular arrangement of [Cu(dmdt)22]]

Cu….tetrahedral coordinationThe dihedral angle between the ligand planes is 80.3

Projection of ligand layer along the molecular long axis

[Cu(dmdt)2]

C= 0.327 emu K mol-1-4.18 K 84% S =1/2 spin

g = 2.035 (ESR)

Molecular Structure of [Zn(tmdt)2] and [Cu(dmdt)2]

Crystal Data for [Zn(tmdt)2]Monoclinic, C2/ca = 25.3284(2) Åb = 8.06737(6) Åc = 11.35959(8) Å

= 92.711(1)°Z = 4V = 2318.54(5) Å3Rwp, RI = 0.021, 0.058

[Zn(tmdt)2]Dihedral angle around Zn: 89.63

[Cu(dmdt)2]Dihedral angle around Cu: 80.29

a bc

d e

f

g hi

[Zn(tmdt)2] [Cu(dmdt)2]

a (Å) 2.326 2.276b (Å) 1.767 1.692c (Å) 1.368 1.414d (Å) 1.757 1.745e (Å) 1.755 1.745f (Å) 1.353 1.341g (Å) 1.718 1.741h (Å) 1.728 1.754i (Å) 1.334 1.323

( ) 94.21 92.87

K. Yamamoto et al. (Univ. of Tokyo)

Band Calculation and Properties of [Zn(tmdt)2]

0 2 4 6 8 10DOS (arb. units)

Ene

rgy

(eV

)

-0.2

0.2

X Y Z

Compressed pellet

100 200 300

0

-0.2

0.2

F

Ene

rgy

(eV

)

104

1

rt = 1.6 x 10-2 S·cm-1Ea = 146 meV

Semiconducting behavior

0

F

Temperature (K)

Nor

mal

ized

resi

stiv

ity

103

102

101

Y. Okano(IMS)

Magnetic Properties of [Zn(tmdt)2]

0 100 200 300

s (a.

u.) s T

(a. u.)

T (K)

10203040506070

2.0002.0022.0042.0062.0082.010

0 100 200 300

Hpp g

T (K)

T (K)0 100 200 300

0.5

0.4

0.3

0.2

0.1

0

T(e

mu·

K·m

ol-1

)

[Zn(tmdt)2]p = 1.3 x 10-4 emu·K·mol-1 at T > 230 K

[Cu(dmdt)2]p = 3.8 x 10-4 emu·K·mol-1 at T > 100 K

[Zn(tmdt)2]

[Cu(dmdt)2]

SQUID ESR

10 kOe

Structure Determination of [Co(dt)2]

Y. Fujishiro, E. Nishibori, M. Takata and M. Sakata (Nagoya Univ.)

SPring 8 BL02B2: Powder X-ray diffraction

Rwp = 5.3%

RI = 8.2%

S

S

S

S

SCo

S

S

S

S

S

S

S

S

S

S

S

SCo

S

S

S

S

S

S

S

4601points(2 4o-50o, 0.01ostep)

SPring-8 BL02B2

Molecular Structure of [Co(dt)2]

Co1

Co1

S1

S2

S3

S4

S5

S6S7

S8

S9

S10

C11

S12

Co1

Co1S1*

S1

Co1···Co1*: 3.275 Å

Dimerized structure with intermonomer Co-S bridgeThere are many S···S contacts in the dimer

6.6

1.3

6.6

12.4

8.1

12.3

11.5

7.5

5.8

5.0

2.2

3.374 Å3.352 Å3.669 Å

3.479 Å3.479 Å3.246 Å

3.352 Å

3.374 Å3.669 Å

3.479 Å3.246 Å

Crystal data for [Co(dt)2]TriclinicSpace group: P-1a = 11.7185(3) Åb = 10.9513(2) Åc = 7.7336(1) Å

= 79.737(2)= 96.474(2)= 113.973(2)

V = 891.45(7) Å3Z = 2Rwp = 5.3 % RI = 8.2 %

S

S

S

S

SCo

S

S

S

S

S

S

S

S

S

S

S

SCo

S

S

S

S

S

S

S

Co-S 2.425 Å Co-S-Co 90.516o2.1862.1662.1722.179

E. Fujiwara et al. (Univ. of Tokyo)

Crystal Structure of [Co(dt)2]

0bc

a 0

b

c

a3.448 Å

3.431 Å3.647 Å

3.489 Å

3.504 Å3.489 Å

3.647 Å

3.431 Å

3.448 Å

3.485 Å

3.318 Å

3.318 Å

Crystal Data for [Co(dt)2]TriclinicSpace group: P-1a = 11.7185(3) Åb = 10.9513(2) Åc = 7.7336(1) Å

= 79.737(2)= 96.474(2)= 113.973(2)

V = 891.45(7) Å3Z = 2Rwp = 5.3 % RI = 8.2 %

Physical Properties of [Co(dt)2]

100 200 30000

5

10

15

/rt

0.1 1 10 1000.1

1

10

100

MAGNETIC SUSCEPTIBILITYdown to 1.9 K

Polycrystalrt = 3.5 x 10-4 emu·mol-1

100 200 3000Temperature (K)

100 200 3000

5 kOe

(em

u·m

ol-1

)

0

0.5

1.0

(x 10-2)1.5

0

0.1

0.2

T(e

mu·

K·m

ol-1

)

C= 0.03emu·K·mol-11.6 % 3/2 spins ( = -1.3 K)

Temperature (K)

CONDUCTIVITY down to 0.55 KCompressed pellet sample

rt = 19 S·cm-1 , 0.55K/ rt 1/10

0.3

Fermi Surfaces of [Co(dt)2]

S

S

S

S

SCo

S

S

S

S

S

S

S

S

S

S

S

SCo

S

S

S

S

S

S

S

Summary

Ni(tmdt)2 First Single-component Molecular Metal

Au(tmdt)2 Metallic from 300 K to 4 KAntiferromagnetic Phase Transition at 110 K

Cu(dmdt)2 Highly Conducting Paramagnetic MoleculeSemimetal or Zero-gap Semiconductor

Zn(tmdt)2 Nonmagnetic, Semimetal

[Co(dt)2]2 Dimeric Molecule, Pauli-paramagnetic Metal

Syntheses and characterizationB. Zhou (Nihon Univ.)E. Fujiwara, B. Zhou, S. Shimamura, W. Suzuki, K. Yamamoto (Univ. of

Tokyo) H. Kobayashi, Y. Okano, H. Fujiwara, H. Cui, K. Takahashi (IMS)H. Tanaka(AIST)Synchrotron radiation powder diffractionY. Fujishiro, E. Nishibori, M. Sakata (Nagoya Univ.)M. Takata (SPring-8)1H-NMRK. Miyagawa, Y. Hara, K. Kanoda (Univ. of Tokyo)1st principle band structure calculationS. Ishibashi (AIST), K. Terakura(Hokkaido Univ., JAIST)H. Tanaka, S. Hara, M. Tokumoto (AIST)Magnetic quantum oscillationsH. Tanaka. M. Tokumoto(AIST)J. S. Brooks, D. Graf, E.S. Choi (NHMFL, Florida State Univ.)S. Yasuzuka(NIMS)XPS and NEXAFSH. Kondo, T. Ohta (Univ. of Tokyo)

Acknowledgments